Water-insoluble azodyestuffs and fiber dyed therewith



Patented Nov. 16, 1937 I WATER-INSOLUBLE AZODYESTUFFS AN FIBER 'DYEl) 'rrn nnwrrn Heinrich Morschel, Leverkusen-Wiesdorf, and

Felix Gund, Cologne-Deutz, Germany, assignors to General Aniline Works,-Inc.,- New York,

N. Y., a corporation of Delaware N0 Drawing. Application November 7, 1935, Se-

rial No. 48,776; In 1934 12 Claims.

The present invention relates to new water-insoluble azodyestuffs, more particularly it relates to azodyestuffs which may be represented by the following general formula: I

wherein It stands for an aromatic radical free -v Q from groups inducing solubility in water, such as a benzene or naphthalene nucleus, which may bear suitable substituents, such as alkyl, alkoxy, I halogen, the nitro group, the trifluoromethyl,

group, and Ri stands for the radical of an arylamide, of a p-ketocarboxylic acid or of an arylamide of an o-hydroxycarboxylic acid, which has been coupled in o-position to the hydroxy group. Our new dyestuffs are obtainable by diazotizing an aminoazo compound of the general for- 1' i mula:

wherein R means the same as stated above, and

I shades of good fastness properties.

The aminoazo compounds used as diazotizatio components in the manufacture of our new dye- I stuffs areobtainable for example by coupling in 5939,11 alkaline medium a 7-hydroxy-1 'acylaminodistinctionthereto according to the process as Germany November 14,

(01. zeoess) naphthalene which may be represented by the following formula:

NHCOX wherein X means alkoxy or aryloxy, the amino group, in which one or both hydrogen atoms may be substituted by aliphatic or aromatic radicals, a hydrogen atom, alkyl, aralkyl, aryl or hydroaryl, with a diazo compound free from groups inducing solubility in water, and splitting off the acyl group in the 1-position according to methods known per se. This method of preparing the diazotization components is of especial value for the manufacture of those aminoazo compounds of the above identified type, in which the arylaz o group in the 8-position is derived from amines of a high energy of coupling, i. e. of strongly negative substituted amines, such as arylamines substituted by a nitro group or by at least two halogen atoms. For,.if there is coupled in an alkaline medium 'Z-hydroxy-l-aminonaphthalene with a diazo compound of such an amine of high energy of coupling, besides 8-arylazo compounds there are obtained other coupling products in considerable quantities. In contradescribed. above there are obtained in smooth --reaction and in a uniform manner the corresponding 8-arylazo-7-hydroxy-l-aminonaphthalene. I

The invention is illustrated by the following 35 I examples, butisnot restricted thereto:

Examples 50 grams of cotton yarn are impregnated for half an hour in 'a bath, at 30? 0. prepared in'the usua-l manner and containing per litre 3 grams of 2-' (2-hydroxynaphthalene 3,- carbonylamino) .5-chloro-l-methoxybenzene, 8 cos. of aqueous caustic soda lye of 38 B. and 6 cos; of Turkey red oil. The yarn ris squeezed, and'the dyeing is developed by introducing theyarn into one litre of a developing bath containing 2.65 grams of diazo-q "'tized 8-benizeneazol -amino-7-hydroxynaphthal'ene, 1.5ccs. of gl'acial-aceticacid and 30 grams of '1, common salt. After rinsing,'soaping in a boiling 9' I bath, again rinsing and drying, there is obtained a deep brown; the dyestuff corresponds probably to the following formula:

iii? NN In an analogous manner there is obtained from diazotized:

8- 2-nitropheny1azo) 7-hydroxy-1-aminonaphthalene benzene 8-(2-nitrophenylazo)-7-hydroxy-l-aminonaphthalene 2-(2 hydroxynaphthalene 3 carbonylamino) 5 methoxy-l- Do. 8 (2 ethoxyphenylazo) 7 hydroxy-l-aminonaphthalene droxy-l-amino-naphthalene 8- (4--methoxyphenylazo) 7 hy droxy-l-aminonaphthalene 8 (2 methy-lphenylazo) 7 hy drgiy-l-aminonaphthalene 8 (4 methylphenylazo) 7 hy droxy-l-aminonaphthalene 8 (3 chloro 4- methoxyphenyl azo) 7 hydroxy 1 amino naphthalene '8 (2 chlorophenylazo) 7 hy droxy-l-aminonaphthalene OCH;

| l HO hONHQ-m 2 (2'-hydroxynaphthalene3- carbonylamino) -1-methyl- 8 2'-nitrophenylazo) 7-hydroxy-1-amin0napl1- thalene methylbenzene a blackish brown, the dyestuff corresponding to the following formula:

OH ONHGO OH:

1 (2 hydroxynaphthalene 3 carbonylaminoy naphthalene 2 (2 hydroxynaphthalene 3 carbonylamino)-1-ethoxy-benzene terephthaloyl diacetic acid di (2 methoxy- 4 1 ehloro 5 methyl 1 phenylamide) 1 -(l, 2 benzocarbazole 2 hydroxy 3-earbonylamino)-4-methoxybenzene 3, 3 dimethyl 4, 4 diaeetoacetyldiphenyl 2 (2 'hydroxynaphthalene 3 carbonylamino)-1-methylbenzene 2 (2 hydroxynaphthalene 3 carbonylamino)-1, 4-dimethoxybenzene B- (2 -hydroxynaphthalene 3 carbonylamino) l-methoxybenzene I 4- (2f-hydroxynaphthalene-3-carbonylamino) -2- chloro-l-methoxybenzene 2-(2-hydroxynaphthalene-3-carbony1amino)-1- 2- (2-hydroxynaphthalene'-3-carbonylamino) -1- methyl-5-ehlorobenzene 1 (2 hydroxynaphthalene 3 carb onylamino) naphthalene 2-(2-hydroxynaphtha1ene-3-carbonylamino) -1- 'methoxybenzene a yellowish blackish brown, the dyestuif coir sponding to the following formula:

2 (2-hydroxynaphthalene-8- carbonylamino) -Lmethoxybenzene a yellowish'blackish brown, the dyestuff corresponding to the following formula:

21 blackish brown an olivish dark brown a reddish brown a dark brown a reddish brown a dark brown a reddish dark brown a reddish dark brown a violettish blackish brown a reddish dark brown a reddish dark brown a violettish reddish brown a reddish dark brown a reddish dark brown a reddish brown a brown a reddish brown a'reddish brown a dull reddish brown a yellowish brown 8 (3 chlorophenylazo) 7- by drgry-I-aminonaphthalehe 8-(2-chlore-6'-methyl-phenylazo)- Hgdroxy-l-aminonaphthalene 8-(3'-ehloro-6'-methoxyphenylazo) -7-:%ydroxy-1-aminonaphthalene 8-(4' chlorophenylazo) -7-hydroxy l-aminonaphthalene 8-(2, 4-dimethylphenylazo)-7-hydrgy-l-aminonaphthalene 8-(2' -nitrophenylazo)-7-hydroxy-1- aminonaphthalene I 8-(3-nitrophenylazo) -7-hydroxyl-aninonaphthalene hygroxy-l-aminonaphthalene s- (a' -nitro-4, fi-dimethylphenylazo)-7-hydroxy-1-aminonaphtha i? I 8 (3' nitro 4 methylphenylazo) 7-1]i)ydroxy-l-aminonaphthelene 8-(2'-methoxy-4'-nitrophenylazo)- 7-?)ydroxy-l-aminonaphthalene 8- (3-nitro-6' -methylpheny1azo) 7-hydroxy-1-arninonaphthalene Do. I

8-(3-nitro-6-ethoxyphenylazo)-7- hydroxy-l-aminonaphthalene 8- (3'-nitro-4' -ethoxyphenylazo) 7-hydroxy-l-aminonaphthalene 8-(2'-nitro-4'-methoxyphenylazo)- '7-hydroxy-1-aminonaphthalene S-benzeneazo-1-amino-7-hydroxynaBhthalene 1-amino-7-hydroxynaphthalene Do. 7 p

8 (3 chloro 4' methoxyb enzeneazo) 1 amino 7 hydroxynaphthalene 8-(2'-chlorobenzeneezo)-1-amino-7- hydroxynaphthalene We claim:

1. Waterinsoluble azodyestuffs of the general formula:

2- (2' -hydroxynephthale'ne 3' -carbonylamino) naphthalene 4-(2-hydroxynaphthslene-W-carbonjlamino)-2- chloro-l-methoxybenzene 2- 2'- hydroxynaphthalene-3- carbpnylamino) na phthalene 2-( v-hydroxynaphthalene-3'-carbonylamino)-5- methoxy-I-methylbenmne 2-(2-hydroxynaphthalene-3'-carbonylamino)-6- methoxy-l-methylbenzene 2- (2' -hydroxynaphthalene 3' carbonylamino) na hthale ne 7 1 2-(2 -hydroxynaphthalene-3'-rcarbonylamino) -1- chlororl-methy'lbenzenev 2-(2'-hydroxynaphthalene-ii-carbonylamino)-1- methylbenzene 2-(2-hydroxynaphthaiene-3-carbonylamino)-1- methoxybenzene 2-(2-hydroxynaphthalene-3-carbonylamino)-1- rethoxybenzene 2-(2'-hydrorynaphthalene-3-oarbonylamino)-1,

4-dimethoxybenzene 1- (Zf-hydroxynaphthalene-W- carbonylaminoinaphthalene V 2- (2' -hydroxynaphthalene- 3- carbonylamino) 1-methoxybenzene 2-, (2 -hydroxynaphthalene -3- carbonylamino) 5ethoxy-1-methy1henzene 2- (2 hydroxynaphthalene 3i carbonylamino) lA dimethoxybenzene 2- (2' hydroxynaphthalene 3' carbonylamino) naphthalene 2-(-hydroxynaphthalene-3' -carbonylamino) 1 methoxybenzene 7 2- (2' hydroxynaphthalene 3' carbonylamino) 'l-methylbenzene 2-(2-hydroxynaphthalene-3-carbonylamino)-1- methylbenzene' 4- (2 -hydroxynaphthalene-3'- carbonylamino) 1.3-dimethylbenzene 2-(2'-hydroxynaphthalene-3-carbony1amino)-4- chloro-l-methoxybenzene 2-(2-hydroxynaphthalene-3'-carhonylammo)-5- methoxy-l-methylbenzene 2-(2-11ydroxynaphthalene 3 -carboriylemino)-1- methylbenzene 2-(2-hydroxynaphthalene-3-carbonylamino)-1- e methoxybenzene 2-(2-hydroxynaphthalene-3'-carbonylamino)-5- methoxy-l-methylbenzene 1 (2 -hydroxynaphthaiene 3' carbonylamino) naphthalene 2-(2' -hydroxynaphthalene-3f-carbonylamh1o) -1- ethoxybenzene 3, 3-dimethyl-4, 4-diacetoacetylaminodiphenyl 2-(2'-liydroxynaphthalene-3'-carbonylaniino);1,

4-d1methoxybenzene 1 (2- hydroxynaphthalene 3' carbonylamino) naphthalene 2-(2'-hydroxynaphthalene-3'-carbony1am1no) -6- chloro-l-methylb enzene 2 hydroxynaphthalene 3 carbonylsminobenzene properties.

2. Waterinsoluble azodyestufis of the general formula:

wherein R stands for aryl and R1 stands for a member selected from the group consisting of the radical of an arylamide of a fl-ketocarboxylic acid and of an arylamide of an o-hydroxycarboxylic acid which has been coupled in o-position a reddish dark brown a reddish dark brown a violettish dark brown s violettish darir brown a yellowish dark brown a reddish dark brown a reddish 1 a reddish brown a dark brown 8. violettish dark brown a reddish blackish'brown a brown I a reddish dark brown a dark brown a reddish dark brown in brown a reddish brown a reddish brown a brown a reddish brown 7 areddishdarl: brown a reddish dark brown a dark brown a reddish brown a reddish brown a violettish dark brown a blackish brown a reddish blackish brown a reddish brown a reddish dark brown a reddish-violettish dark brown 7 a reddish dark brown a yellowish dark brown an orange brown 7 a yellowish dark brown a brown a brown a reddish dark brown a reddish brown to the hydroxy group, yielding when produced on the fiber various shades of good fastness wherein R stands for a member selected from the group consisting of phenyl and alkyl-, 75

alkoxy-, halogenand nitro-substi tuted' phenyl and R1 stands for a member :selected fromthe group consisting of the radical of an arylamide 5. The dyestufi of the formula of a ,B-ketocarboxylic acid and of'an arylamide of an o-hydroxycarboxylic acid which has been coupled in o-position to the hydroxy group, yielding when produced on the fiber various shades of good fastness properties.

3. Waterinsoluble azodyestuffs of the general formula:

6H CONH-Ri wherein R and R1 stand for members selected from the group consisting of phenyl and .alkyl-,.. alkoxy-, halogenand nitro-substituted phenyl."

claim 1.

yielding when produced on the fiber yellowish blackish-brown :shades of good fastness prop? erties.

6.;The dyestufi of the formula:

OCH;

yielding when produced on the fiber yellowish blackish-brown shades of good fastness properties.

7. Fiber dyed with a dyestufi as claimed in 8. Fiber dyed with a dyestuff as claimed in 7 claim .2.

9. Fiber dyed with a ,dyestuff as claimed in claim 3.

10. Fiber'dyed with a dyestuff as claimed in claim 4.

' 11. Fiber dyed with the dyestuff as claimed in claim 5.

12. Fiber dyed with the dyestuff as claimedin claim '6.

- HEINRICH MORSCHEL.

FELIX GUND. I

DISCLAIMER 2,099,272.Heinrich Morschel, Leverkusen-Wiesdorf, and Felix Gund, Cologne- Deutz, Germany. WATER-INSOLUBLE AZODYESTUFFS AND FIBER DYED THEREWITH. Patent dated November 16, 1937. Disclaimer filed January 20, 1939, by the assignee, General Aniline Works, Inc. Hereby enters this disclaimer to claims 1, 2, 3, 7, 8, and 9 of said patent.

[Ofiicial Gazette February 14, 1939.] 

